JPH0157695B2 - - Google Patents
Info
- Publication number
- JPH0157695B2 JPH0157695B2 JP57041622A JP4162282A JPH0157695B2 JP H0157695 B2 JPH0157695 B2 JP H0157695B2 JP 57041622 A JP57041622 A JP 57041622A JP 4162282 A JP4162282 A JP 4162282A JP H0157695 B2 JPH0157695 B2 JP H0157695B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- rubber
- nickel
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 claims description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 68
- 229910052759 nickel Inorganic materials 0.000 claims description 35
- 229920001971 elastomer Polymers 0.000 claims description 30
- 239000005060 rubber Substances 0.000 claims description 29
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001369 Brass Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000010951 brass Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229920003244 diene elastomer Polymers 0.000 claims 2
- 239000010941 cobalt Substances 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- 238000009472 formulation Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000004148 curcumin Substances 0.000 description 5
- 150000002902 organometallic compounds Chemical class 0.000 description 5
- 150000001869 cobalt compounds Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- -1 nickel organic compounds Chemical class 0.000 description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- FQOKARXJRRGQDN-UHFFFAOYSA-L 4-aminobenzoate;cobalt(2+) Chemical compound [Co+2].NC1=CC=C(C([O-])=O)C=C1.NC1=CC=C(C([O-])=O)C=C1 FQOKARXJRRGQDN-UHFFFAOYSA-L 0.000 description 1
- JOSYJMYICHDBJR-UHFFFAOYSA-L 4-aminobenzoate;nickel(2+) Chemical compound [Ni+2].NC1=CC=C(C([O-])=O)C=C1.NC1=CC=C(C([O-])=O)C=C1 JOSYJMYICHDBJR-UHFFFAOYSA-L 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- YXBBHUHVQZEWOK-UHFFFAOYSA-N cobalt;ethyl acetate Chemical compound [Co].CCOC(C)=O YXBBHUHVQZEWOK-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- JLRHAYPLRSZUPL-UHFFFAOYSA-N ethyl acetate;nickel Chemical compound [Ni].CCOC(C)=O JLRHAYPLRSZUPL-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 229940032017 n-oxydiethylene-2-benzothiazole sulfenamide Drugs 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10S156/91—Bonding tire cord and elastomer: improved adhesive system
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
- Y10T428/31696—Including polyene monomers [e.g., butadiene, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31707—Next to natural rubber
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Reinforced Plastic Materials (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Laminated Bodies (AREA)
Description
本発明は硫黄により硬化し得るゴムを主成分と
する組成物に関する。本発明は、特に硬化中に金
属表面に接着し得る組成物に係る。
硫黄により硬化し得るゴムの金属表面に対する
接着性を改良する目的で、コバルトの有機酸の塩
またはコバルトの複合化合物を使用することは公
知である。同様に、他の金属の有機化合物、例え
ばニツケル、チタン、モリブデンの有機化合物も
提案されていた。有機金属化合物などを含有する
組成物は、特に以下の特許もしくは特許出願に記
載されている：
フランス特許第2198830号、同第2311797号、同
第2368515号、英国特許第1122528号、米国特許第
2912355号、同第3905947号、同第4057529号、同
第4203874号、ヨーロツパ特許出願第3820および
9000号、DD第122255号、日本特公昭49−20072
号（特願昭45−114693号）。
これらの文献に記載されている組成物は以下に
述べる欠点の少なくとも１つを有している。
−製造することが難しく、長時間を要しかつ不経
済な合成に導くような、極めて複雑な式を有す
る有機金属化合物を使用しなければならない；
−硬化後、周囲温度の下で不充分な、金属表面に
対する接着性を有する；
−硬化後、高温度下でエージングした場合に、金
属表面に対する不十分な接着性を有する；
−硬化後に、過度のヒステリシス損を有し、これ
はこのものを使用することが不利となるような
ゴムの発熱を生ずる。
本発明の目的は前記欠点を同時に改善すること
である。本出願人は、これらすべての欠点が硬化
前に、硫黄により硬化し得るゴム組成物にニツケ
ル（）のアセチルアセトネートを添加すること
によつて、克服し得るという思いがけない方法を
見出した。
結果として、本発明の組成物は少なくとも１種
の硫黄によつて硬化し得るゴムを含み、かつ硬化
中に少なくとも１種の金属表面に接着させるため
のものであり、これは更にゴム100重量部当たり
ニツケル（）アセチルアセトネートとして存在
するニツケルを0.1〜２重量部含有することを特
徴とする。
同様に、本発明は少なくとも１種の本発明の組
成物と、少なくとも１面が金属である少なくとも
１種の固体物体とを含む、未硬化集合体にも係
り、ここで該組成物は硬化の際に前記表面と接着
される。本発明はまた該集合体を硬化することを
含む方法並びに該方法によつて得られる物品にも
関する。該硬化された物品は、例えばベルト、
管、空気タイヤの外皮並びに例えばケーブルなど
の強化物質となり得る物質などであり得る。
以下、本発明を非限定的実施例により例示す
る。
実施例 １
本実施例の目的は、硬化後における、コバルト
またはニツケルの有機化合物を含有する10種の組
成物の特性を比較することである。
使用する組成物はすべて以下のような同一の基
本処方物を有する（数値は重量部を表す）。
天然ゴム 100
カーボンブラツクN326 70
酸化亜鉛 ９
酸化防止剤、サントフレツクス（Santoflex）13
１
ステアリン酸 0.5
硫 黄 ７
NOBS 0.6
ただし、「サントフレツクス13」はＮ−ジメチ
ル−１，３−ブチル−N′−フエニル−ｐ−フエ
ニレンジアミンで、Monsanto社の製品である。
またNOBSはＮ−オキシジエチレン−２−ベン
ゾチアゾールスルフエナミドで硬化促進剤として
機能する。
この基本処方物に、コバルトまたはニツケルの
有機化合物を添加する。該化合物の量は、組成物
がエラストマー100重量部当たり、ニツケルまた
はコバルトを0.45部含有するような量である。
かくして参照番号C1〜C10で区別される10種の
組成物が得られ、該組成物各々は以下のようなコ
バルトまたはニツケル化合物の性質によつて特徴
ずけられる。
C1：ナフテン酸コバルト
C2：ナフテン酸ニツケル
C3：酢酸コバルト
C4：酢酸ニツケル
C5：コバルトのアセチルアセトネート
C6：ニツケルのアセチルアセトネート
C7：ｐ−アミノ安息香酸コバルト
C8：ｐ−アミノ安息香酸ニツケル
C9：エチル酢酸コバルト
C10：エチル酢酸ニツケル
＊これら化合物において金属の原子価はであ
る。
かくして、C6組成物が唯一の本発明の組成物
である。
更に参照番号C0として、コバルトまたはニツ
ケルの誘導体をまつたく含まない基本処方物に相
当するものを使用する。
これら組成物の各々によつて、試験片を作成
し、その中には亜鉛または鎮鍮で被覆された１cm
の鋼繊維が包み込まれており、該繊維の径はその
外層をも含めて1.3mmである。次いでこの試験片
を硬化する。この硬化は全組成物に対して同じ方
法で操作する。即ち、140℃にて60分間維持する。
従つて、各試験片において、該繊維は硬化された
組成物の少なくとも２mmの厚さの層により軸に沿
つて包囲されている。
以下の第１表には、周囲温度即ち約20℃にて該
試験片から外部に前記繊維を引抜くために必要と
される力を、各試験片に対して与えてある。この
引抜力は該繊維が亜鉛によつて被覆されている場
合にはTZで表し、また該繊維が鎮鍮で被覆され
ている場合にはTLで表す。この力はニユートン
で表示してある。
引抜力のいくつかの数値の後に付された文字Ｄ
は、引抜きが初めに密着していた繊維部分の部分
的削剥を伴つて起こることを示す。
第１表には、各組成物に対する以下のような値
をも示してある。
E100：100％伸びにおける弾性率；これはメガパ
スカル（MPa）で表示してあり、次式：
E100＝Ｆ／So×１＋ε／ε
（ただし、Ｆは初期断面積Soを有する試験片
に、100％に等しい即ち比１＋ε／εが２に等しい
相対的伸びεを与えるのに必要な力である）に
従つて決定される；
P60：60℃の温度下で運動エネルギーの一部を与
えつつ変形する振子に対して、試験片によつて
回復されないエネルギー分率（％で表示）：
従つてP60は60℃におけるヒステリシス損の
尺度である。
E100およびP60の値は金属繊維のない試験片に
ついて決定され、該組成物は従つて金属繊維を含
む試験片と同様な条件下で硬化される。
The present invention relates to sulfur-curable rubber-based compositions. The present invention particularly relates to compositions capable of adhering to metal surfaces during curing. It is known to use salts of organic acids of cobalt or complex compounds of cobalt for the purpose of improving the adhesion of sulfur-curable rubbers to metal surfaces. Similarly, organic compounds of other metals have been proposed, such as nickel, titanium, and molybdenum. Compositions containing organometallic compounds and the like are described in particular in the following patents or patent applications: French Patent No. 2198830, French Patent No. 2311797, French Patent No. 2368515, British Patent No. 1122528, United States Patent No.
2912355, 3905947, 4057529, 4203874, European Patent Application No. 3820 and
No. 9000, DD No. 122255, Japan Special Public Service 1972-20072
No. (Special Application No. 114693, Showa 45). The compositions described in these documents have at least one of the disadvantages mentioned below. - have to use organometallic compounds with very complex formulas, which are difficult to produce, lead to lengthy and uneconomical syntheses; - after curing, insufficient - has poor adhesion to metal surfaces when aged under high temperatures after curing; - has excessive hysteresis losses after curing, which makes this material This results in heat generation of the rubber which makes it disadvantageous to use. The aim of the invention is to simultaneously remedy the above-mentioned drawbacks. The applicant has unexpectedly found that all these drawbacks can be overcome by adding nickel () acetylacetonate to the sulfur-curable rubber composition before curing. As a result, the composition of the invention comprises at least one sulfur-curable rubber and is intended for adhesion to at least one metal surface during curing, which further comprises 100 parts by weight of rubber. It is characterized by containing 0.1 to 2 parts by weight of nickel present as nickel () acetylacetonate. The invention likewise relates to uncured assemblies comprising at least one composition of the invention and at least one solid object having at least one side metal, wherein the composition is cured. At the same time, it is bonded to the surface. The invention also relates to a method comprising curing said aggregate, and to an article obtained by said method. The cured article may be, for example, a belt,
It can be a tube, the skin of a pneumatic tire, or a material that can serve as a reinforcing material, for example a cable. The invention is illustrated below by means of non-limiting examples. Example 1 The purpose of this example is to compare the properties of ten compositions containing cobalt or nickel organic compounds after curing. The compositions used all have the same basic formulation as follows (numbers represent parts by weight): Natural rubber 100 Carbon black N326 70 Zinc oxide 9 Antioxidant, Santoflex 13
1 Stearic acid 0.5 Sulfur 7 NOBS 0.6 However, "Santoflex 13" is N-dimethyl-1,3-butyl-N'-phenyl-p-phenylenediamine and is a product of Monsanto.
Further, NOBS is N-oxydiethylene-2-benzothiazole sulfenamide and functions as a curing accelerator. To this basic formulation, an organic compound of cobalt or nickel is added. The amount of the compound is such that the composition contains 0.45 parts of nickel or cobalt per 100 parts by weight of elastomer. Ten compositions are thus obtained, distinguished by the reference numbers C1 to C10, each characterized by the properties of the cobalt or nickel compound as follows. C1: Cobalt naphthenate C2: Nickel naphthenate C3: Cobalt acetate C4: Nickel acetate C5: Cobalt acetylacetonate C6: Nickel acetylacetonate C7: Cobalt p-aminobenzoate C8: Nickel p-aminobenzoate C9: Cobalt ethyl acetate C10: Nickel ethyl acetate *The valence of the metal in these compounds is. Thus, the C6 composition is the only composition of the invention. Furthermore, reference number C0 is used which corresponds to the basic formulation which does not contain any derivatives of cobalt or nickel. With each of these compositions test specimens were prepared in which a 1 cm
The diameter of the fibers including the outer layer is 1.3 mm. The specimen is then cured. This curing is operated in the same manner for all compositions. That is, it is maintained at 140°C for 60 minutes.
Thus, in each specimen the fibers are surrounded along the axis by a layer of at least 2 mm thick of the cured composition. Table 1 below provides for each specimen the force required to pull the fibers out of the specimen at ambient temperature, approximately 20°C. This pulling force is expressed as TZ if the fiber is coated with zinc and TL if the fiber is coated with brass. This force is expressed in Newtons. The letter D after some numerical values of withdrawal force
indicates that pull-out occurs with partial ablation of the fibers that were initially in close contact. Table 1 also shows the following values for each composition: E100: Elastic modulus at 100% elongation; this is expressed in megapascals (MPa) and is expressed by the following formula: E100=F/So×1+ε/ε (where F is the elasticity of the specimen with initial cross-sectional area So %, i.e. the ratio 1 + ε/ε is the force required to give a relative elongation ε equal to 2); P60: Deformation while imparting part of the kinetic energy at a temperature of 60 °C The fraction of energy (expressed in %) that is not recovered by the specimen for a pendulum that The values of E100 and P60 are determined for specimens without metal fibers, and the composition is therefore cured under similar conditions as specimens containing metal fibers.
【表】
この第１表の値は以下のように考察することを
可能とする。
１ 有機金属化合物を含まない組成物C0はかな
り低いもしくはかなり低い部類にはいる引抜力
TZおよびTLに導く。
２ 弾性率E100は殆ど同じ大きさである。
３ すべてのコバルト化合物は、極めて近い引抜
力TZまたはTLを示す化合物に導き、これらの
力は1000〜1200ニユートンの範囲内に含まれ
る。
４ ニツケル化合物の中で、ニツケル（）のア
セチルアセトネート（本発明による組成物C6）
のみが高い引抜力を与えており、この力はコバ
ルト化合物について得られた値と殆ど同様な大
きさの値であるか、鎮鍮繊維の場合と同様にす
ぐれている。他のすべてのニツケル化合物は、
コバルトの有機化合物について得られた値より
も極めて低い引抜力に導く。これは、特に亜鉛
で被覆された繊維上での接着の場合（TZ）に
相当する。この事実は、ニツケルとコバルトと
が元素周期率表において近接した位置を占めて
いるという意外な事実を示している。実際のと
ころ、同じ有機基を含むコバルトおよびニツケ
ルの有機化合物はほぼ匹敵する接着力に導くこ
とを予想することができよう。
５ 夫々、有機金属化合物を含有する組成物C1
〜C10の中で、本発明による組成物C6ではヒス
テリシス損が極めて低い水準に抑えられてお
り、有機金属化合物を含まない組成物C0に対
するのと全く同様である。１例として、同じ有
機基（アセチルアセトネート）を含む組成物
C5、C6について得られた結果を比較すると、
コバルトをニツケルに変えることにより、同じ
弾性率について、ヒステリシス損を20％減ずる
ことができることを示しており、これは極めて
実質的な改良に相当する。この事実は、コバル
トとニツケルが元素周期律表において隣接位置
を占めているという事実からは予想し得ないこ
とである。ヒステリシス損を減じることは重要
なことである。というのは、これが対応する物
品に加工する際に、ゴムの加熱を生じるからで
ある。この加熱は前記物品の急速な破損に導く
可能性がある。この現象は、特に空気タイヤ外
皮において著しく、更に重量自動車用もしくは
土木工学エンジン用空気タイヤ外皮において著
しい。後者は著しい発熱に対して敏感であり、
従つて使用の際の硬化物の連続的変形に対して
敏感である。本発明によるニツケル（）のア
セチルアセトネートの使用は、特にこれら物品
の耐用寿命を増大することを可能とする。
実施例 ２
本実施例では、コバルトおよびニツケル以外の
金属のアセチルアセトネートの作用を示す。実施
例１に与えた基本的処方物に、得られる組成物が
金属を0.45重量部含有するような量で該金属のア
セチルアセトネートを添加する。かくして参照番
号C11〜C14で示される４種の組成物を得、該組
成物の各々は以下の如きアセチルアセトネートの
性質によつて特徴ずけられる。
C11：銅（）のアセチルアセトネート
C12：鉄（）のアセチルアセトネート
C13：バナジウム（）のアセチルアセトネート
C14：マンガン（）のアセチルアセトネート
以下の第２表に、これら組成物を硬化した後に
得られる特性を与えた。記号E100、P60、TZお
よびTLは実施例１において示した定義と同じで
ある。[Table] The values in Table 1 can be considered as follows. 1 Composition C0 that does not contain organometallic compounds has a very low or very low pullout force
Lead to TZ and TL. 2 The elastic modulus E100 is almost the same size. 3 All cobalt compounds lead to compounds exhibiting very close pull-out forces TZ or TL, these forces falling within the range of 1000-1200 Newtons. 4 Among the nickel compounds, acetylacetonate of nickel () (composition C6 according to the invention)
only give high pull-out forces, which are almost as large as the values obtained for the cobalt compounds, or as good as those for the brass fibers. All other nickel compounds are
leading to much lower pull-out forces than the values obtained for organic compounds of cobalt. This is particularly the case for adhesion on zinc-coated fibers (TZ). This fact indicates the surprising fact that nickel and cobalt occupy close positions in the periodic table of elements. In fact, one could expect that cobalt and nickel organic compounds containing the same organic groups would lead to approximately comparable adhesion forces. 5 Composition C1 each containing an organometallic compound
-C10, the composition C6 according to the invention has a hysteresis loss suppressed to an extremely low level, which is exactly the same as that for the composition C0, which does not contain an organometallic compound. As an example, compositions containing the same organic group (acetylacetonate)
Comparing the results obtained for C5 and C6,
It has been shown that by replacing cobalt with nickel, the hysteresis loss can be reduced by 20% for the same modulus, which corresponds to a very substantial improvement. This fact is unexpected from the fact that cobalt and nickel occupy adjacent positions in the periodic table of elements. It is important to reduce hysteresis losses. This is because this results in heating of the rubber during processing into the corresponding articles. This heating can lead to rapid failure of the article. This phenomenon is particularly pronounced in pneumatic tire skins, and even more so in pneumatic tire skins for heavy motor vehicles or civil engineering engines. The latter are sensitive to significant heat generation;
Therefore, it is sensitive to continuous deformation of the cured product during use. The use of nickel acetylacetonate according to the invention makes it possible in particular to increase the service life of these articles. Example 2 This example shows the effect of acetylacetonates of metals other than cobalt and nickel. To the basic formulation given in Example 1, the acetylacetonate of the metal is added in such an amount that the resulting composition contains 0.45 parts by weight of the metal. Four compositions, designated with reference numbers C11 to C14, are thus obtained, each of which is characterized by the properties of the acetylacetonate as follows. C11: Acetylacetonate of copper () C12: Acetylacetonate of iron () C13: Acetylacetonate of vanadium () C14: Acetylacetonate of manganese () Table 2 below shows that after curing these compositions: given the properties obtained. The symbols E100, P60, TZ and TL have the same definitions as shown in Example 1.
【表】
この表は、銅、鉄、バナジウム、マンガンのア
セチルアセトネートが各試験に対して繊維の削剥
を伴い、極めて不十分な引抜力を与えることを示
している。
ニツケル（）のアセチルアセトネートの使用
が同時に良好な接着力と低いヒステリシス損とを
与え得るという事実は、特に鉄並びに銅が元素周
期律表においてニツケルと近接した位置を占めて
いるのであるから、予想外のことである。
実施例 ３
本実施例は、ニツケル（）アセチルアセトネ
ートの種種のゴム混合物に対する作用を調べるこ
とを目的とするものである。
実施例１で与えられた基本処方物を、各場合に
おける天然ゴム100重量部を、天然ゴム50部と合
成ゴム50部との混合物で置き代えることにより変
更した。かくして得た種々の処方物に等量のニツ
ケル（）アセチルアセトネートを添加して参照
番号C61〜C63で示される３種の組成物を得た。
これら組成物の各々はニツケル0.45部を含有す
る。（これら部はすべて重量部である）。これら三
種の組成物はこれらが含む合成ゴムの性質によつ
て区別され、夫々以下のような合成ゴムを含有す
る。
C61：スチレン−ブタジエン含有
C62：ポリブタジエン含有
C63：ポリイソプレンゴム含有
下記第３表に、これら組成物を硬化した後に得
られた物性を示す。記号E100、P60、TZおよび
TLは実施例１および２記載のものと同じである。Table: This table shows that copper, iron, vanadium, and manganese acetylacetonates give very poor pullout forces for each test, with abrasion of the fibers. The fact that the use of acetylacetonate of nickel () can give at the same time good adhesion and low hysteresis losses is particularly important since iron and copper occupy a close position with nickel in the periodic table of the elements. This is unexpected. Example 3 The purpose of this example was to investigate the effect of nickel () acetylacetonate on various rubber mixtures. The basic formulation given in Example 1 was modified by replacing 100 parts by weight of natural rubber in each case with a mixture of 50 parts of natural rubber and 50 parts of synthetic rubber. Equal amounts of nickel () acetylacetonate were added to the various formulations thus obtained to obtain three compositions designated with reference numbers C61 to C63.
Each of these compositions contains 0.45 parts of nickel. (All parts are by weight). These three types of compositions are distinguished by the properties of the synthetic rubbers they contain, and each contains the following synthetic rubbers. C61: Contains styrene-butadiene C62: Contains polybutadiene C63: Contains polyisoprene rubber Table 3 below shows the physical properties obtained after curing these compositions. Symbols E100, P60, TZ and
TL is the same as described in Examples 1 and 2.
【表】
この第３表は、これら組成物の引抜力が満足で
きるものであり、かつ削剥を生じないことを示
す。
硬化後、100℃にて48時間のエージング処理に
付した試験片について、TZ、TL、P60の値を周
囲温度条件下で測定する場合において該試験片が
一方で天然ゴムまたは前記の如き硫黄により硬化
し得るゴム混合物と、他方で実施例１に記載した
コバルト化合物、ニツケル（）のアセチルアセ
トネートを、実施例１および３で示したような割
合で含む組成物から作成された場合、以下の事実
が確認される。
−各試料に対する引抜力TZおよびTLの値はエー
ジング前に測定された値と大きさにおいて同等
である。
−ニツケル（）のアセチルアセトネートを含有
する組成物から得られた試験片は極めて低いヒ
ステリシス損を有し、これは同じ組成でかつコ
バルト化合物を含む試験片について測定された
ヒステリシス損の約20％を減ずる。これらすべ
ての測定はエージング後周囲温度条件下で行わ
れた。エージングしてない試験片に対して実施
例１で記載した、ヒステリシス損におけるニツ
ケル（）のアセチルアセトネートの有益な効
果はエージング後においても維持される。
本発明による組成物は充填剤、硬化促進剤また
は種々の添加剤を含むことができ、実施例１に与
えた基本処方物により何等制限されるものではな
い。
本発明による組成物においては、ニツケル
（）のアセチルアセトネートとして存在するニ
ツケルの量は、ゴム100重量部当たりニツケル0.1
〜２重量部なる範囲で変えることができる。とい
うのは、ゴム100重量部当たりニツケルが0.1重量
部に満たない場含には、引抜力は不十分であり、
かつゴム100重量部当たり２重量部を越える場合
には、引抜力がニツケルをそれ以下で含むものに
ついて得られる値よりも高くなることはなく、経
済的理由からニツケル（）アセチルアセトネー
トとしてニツケルを増加することは好ましくない
からである。ニツケル（）アセチルアセトネー
トとして存在するニツケルの量は、好ましくはゴ
ム100重量部当たりニツケル0.2〜１重量部の範囲
で変え得る。本発明による組成物が酸化亜鉛を含
む場合には、酸化亜鉛の量は好ましくはゴム100
重量部当たり３〜80重量部の範囲内で変えること
ができ、かつ有利にはゴム100重量部当たり５〜
15重量部である。
硫黄の量は、好ましくはゴム100重量部当たり
１〜10重量部の範囲内で変えることができ、有利
にはゴム100重量部当たり３〜７重量部である。
本発明による組成物中においてステアリン酸を
使用する場合、その量はゴム100重量部当たり0.1
〜３重量部の範囲内で変えることが好ましく、有
利にはゴム100重量部当たり0.2〜１重量部であ
る。
前記実施例において、金属繊維は完全に鎮鍮ま
たは亜鉛であり得ることは当然である。本発明に
よる組成物の有益の効果は、鎮鍮または亜鉛の金
属表面以外の、例えば銅、鋼の表面においても実
現することができる。
更に、本発明による組成物を接着し得る金属表
面は、場合によつては例えば鉱物材料、特にガラ
ス、もしくは有機ポリマー、特にプラスチツク材
料上に適用することもできる。
勿論、本発明は前記の製造例により何等限定さ
れるものではなく、本発明の範囲を逸脱すること
なしに製造の他の方法並びに形式を見出すことが
可能であるものと理解すべきである。Table 3 shows that the pull-out forces of these compositions are satisfactory and do not cause abrasion. When the TZ, TL, and P60 values are measured under ambient temperature conditions for specimens that have been aged for 48 hours at 100°C after curing, the test specimens are When made from a composition comprising a curable rubber mixture and on the other hand acetylacetonate of the cobalt compound described in Example 1, Nickel () in the proportions as given in Examples 1 and 3, the following: The facts are confirmed. - The values of the pull-out forces TZ and TL for each sample are comparable in magnitude to the values measured before aging. - Specimens obtained from compositions containing acetylacetonate of Nickel (2017) have extremely low hysteresis losses, which are approximately 20% of the hysteresis losses measured for specimens of the same composition and containing cobalt compounds. decrease. All these measurements were performed under ambient temperature conditions after aging. The beneficial effect of Nickel () acetylacetonate on hysteresis loss, described in Example 1 for unaged specimens, is maintained after aging. The composition according to the invention can contain fillers, hardening accelerators or various additives and is in no way restricted by the basic formulation given in Example 1. In the composition according to the invention, the amount of nickel present as acetylacetonate of nickel ( ) is 0.1 nickel per 100 parts by weight of rubber.
It can vary between 2 parts by weight. This is because when the amount of nickel is less than 0.1 part by weight per 100 parts by weight of rubber, the pulling force is insufficient.
If the amount exceeds 2 parts by weight per 100 parts by weight of rubber, the pull-out force will not be higher than the value obtained for those containing less nickel, and for economic reasons nickel is used as nickel () acetylacetonate. This is because an increase is not desirable. The amount of nickel present as nickel () acetylacetonate may vary, preferably from 0.2 to 1 part by weight nickel per 100 parts by weight of rubber. If the composition according to the invention contains zinc oxide, the amount of zinc oxide is preferably 100%
can vary within the range from 3 to 80 parts by weight, and advantageously from 5 to 80 parts by weight per 100 parts by weight of rubber.
15 parts by weight. The amount of sulfur can preferably vary within the range from 1 to 10 parts by weight per 100 parts by weight of rubber, advantageously from 3 to 7 parts by weight per 100 parts by weight of rubber. If stearic acid is used in the composition according to the invention, the amount is 0.1 per 100 parts by weight of rubber.
It is preferred to vary within the range from .about.3 parts by weight, advantageously from 0.2 to 1 part by weight per 100 parts by weight of rubber. Of course, in the above embodiments, the metal fibers can be entirely brass or zinc. The beneficial effects of the compositions according to the invention can also be realized on surfaces other than brass or zinc metal surfaces, for example copper, steel. Furthermore, the metal surfaces to which the compositions according to the invention can be adhered can optionally also be applied, for example, to mineral materials, especially glasses, or organic polymers, especially plastic materials. Of course, it is to be understood that the invention is not in any way limited to the examples of manufacture described above, and that other methods and forms of manufacture can be found without departing from the scope of the invention.
Claims (1)
を含有し、硬化中に少なくとも１つの金属表面に
付着させるための組成物であつて、該組成物が前
記ゴムの他に、ゴム100重量部当たり、0.1〜２重
量部のニツケル（）アセチルアセトネートを含
有することを特徴とする、上記組成物。 ２ 組成物がゴム100重量部当たり、ニツケル
（）アセチルアセトネートの形で存在するニツ
ケルを0.2〜１重量部含有することを特徴とする、
特許請求の範囲第１項記載の組成物。 ３ 組成物がゴム100重量部当たり酸化亜鉛を３
〜80重量部含有することを特徴とする、特許請求
の範囲第１または２項記載の組成物。 ４ 組成物がゴム100重量部当たり酸化亜鉛を５
〜15重量部含有することを特徴とする、特許請求
の範囲第３項記載の組成物。 ５ 組成物がゴム100重量部当たり１〜10重量部
の硫黄を含有することを特徴とする、特許請求の
範囲第１〜４項のいずれか１項に記載の組成物。 ６ ゴム100重量部当たり３〜７重量部の硫黄を
含有することを特徴とする、特許請求の範囲第５
項記載の組成物。 ７ ゴム100重量部当たり0.1〜３重量％のステア
リン酸を含有することを特徴とする、特許請求の
範囲第１〜６項のいずれか１項に記載の組成物。 ８ ゴム100重量部当たり0.2〜１重量％のステア
リン酸を含有することを特徴とする、特許請求の
範囲第７項記載の組成物。 ９ 少なくとも１種のジエン系ゴムを含有するこ
とを特徴とする、特許請求の範囲第１〜８項のい
ずれか１項に記載の組成物。 １０ ジエン系ゴムが天然ゴム、スチレン−ブタ
ジエン、ポリブタジエン、ポリイソプレンからな
る群から選ばれることを特徴とする、特許請求の
範囲第９項記載の組成物。 １１ 金属表面が亜鉛、銅、鎮鍮または剛製であ
ることを特徴とする、特許請求の範囲第１項に記
載の組成物。Claims: 1. A composition comprising at least one sulfur-curable rubber for adhesion to at least one metal surface during curing, the composition comprising, in addition to the rubber, The composition described above contains 0.1 to 2 parts by weight of nickel () acetylacetonate per 100 parts by weight of rubber. 2. characterized in that the composition contains 0.2 to 1 part by weight of nickel in the form of nickel () acetylacetonate per 100 parts by weight of rubber,
A composition according to claim 1. 3 The composition contains 3 parts of zinc oxide per 100 parts by weight of rubber.
The composition according to claim 1 or 2, characterized in that it contains ~80 parts by weight. 4 The composition contains 5 parts of zinc oxide per 100 parts by weight of rubber.
The composition according to claim 3, characterized in that it contains ~15 parts by weight. 5. Composition according to any one of claims 1 to 4, characterized in that the composition contains 1 to 10 parts by weight of sulfur per 100 parts by weight of rubber. 6 Claim 5, characterized in that it contains 3 to 7 parts by weight of sulfur per 100 parts by weight of rubber.
Compositions as described in Section. 7. The composition according to any one of claims 1 to 6, characterized in that it contains 0.1 to 3% by weight of stearic acid per 100 parts by weight of rubber. 8. The composition according to claim 7, characterized in that it contains 0.2 to 1% by weight of stearic acid per 100 parts by weight of rubber. 9. The composition according to any one of claims 1 to 8, characterized in that it contains at least one diene rubber. 10. The composition according to claim 9, wherein the diene rubber is selected from the group consisting of natural rubber, styrene-butadiene, polybutadiene, and polyisoprene. 11. The composition according to claim 1, characterized in that the metal surface is made of zinc, copper, brass or rigid.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8105367A FR2501700B1 (en) | 1981-03-16 | 1981-03-16 | SULFUR VULCANIZABLE RUBBER COMPOSITIONS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57165431A JPS57165431A (en) | 1982-10-12 |
| JPH0157695B2 true JPH0157695B2 (en) | 1989-12-07 |
Family
ID=9256358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57041622A Granted JPS57165431A (en) | 1981-03-16 | 1982-03-16 | Sulfur-curable rubber-major composition |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US4549594A (en) |
| JP (1) | JPS57165431A (en) |
| AR (1) | AR226017A1 (en) |
| AT (1) | AT380690B (en) |
| AU (1) | AU547890B2 (en) |
| BE (1) | BE892320A (en) |
| BR (1) | BR8201429A (en) |
| CA (1) | CA1196436A (en) |
| CH (1) | CH650267A5 (en) |
| DE (1) | DE3209581C2 (en) |
| DK (1) | DK156073C (en) |
| ES (1) | ES510427A0 (en) |
| FR (1) | FR2501700B1 (en) |
| GB (1) | GB2096150B (en) |
| IT (1) | IT1156452B (en) |
| LU (1) | LU84013A1 (en) |
| NL (1) | NL189862C (en) |
| SE (2) | SE451589B (en) |
| ZA (1) | ZA821753B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4719266A (en) * | 1983-03-21 | 1988-01-12 | The Goodyear Tire & Rubber Company | Vulcanization formulations with cobalt compounds |
| DE3635121B4 (en) * | 1985-10-15 | 2004-03-04 | Bridgestone Corp. | Process for producing a rubber-like composite material |
| JP2001114942A (en) * | 1999-10-14 | 2001-04-24 | Sankyo Kasei Kk | Rubber composition, composite material and production of composite material |
| ES2645042T3 (en) * | 2009-09-09 | 2017-12-01 | Bridgestone Corporation | Brass steel cable and composite material of steel-rubber cable, and pneumatic using the same |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US29699A (en) * | 1860-08-21 | Adolph Isaacsen | Construction of apparatus for destroying insects | |
| US2912355A (en) * | 1955-06-20 | 1959-11-10 | Goodrich Co B F | Composition, article and method |
| NL6702910A (en) * | 1966-03-21 | 1967-09-22 | ||
| BE790993A (en) * | 1971-11-09 | 1973-05-07 | Monsanto Chemicals | POLYMERIC MATERIALS WITH THERMALLY REVERSIBLE CROSS-LINKING BONDS |
| JPS4920072A (en) * | 1972-06-17 | 1974-02-22 | ||
| JPS5141915B2 (en) * | 1972-09-08 | 1976-11-12 | ||
| US3903332A (en) * | 1973-02-15 | 1975-09-02 | Uniroyal Inc | Adhesion of polyester to rubber using an adhesive containing added metal compounds |
| US3905947A (en) * | 1973-10-10 | 1975-09-16 | Ciba Geigy Corp | Organo-nickel salts as adhesion promotors for vulcanizable elastomers to metals |
| US3991130A (en) * | 1973-10-10 | 1976-11-09 | Ciba-Geigy Corporation | Organo-nickel salts as adhesion promotors for vulcanizable elastomers to metals |
| JPS51136734A (en) * | 1975-05-22 | 1976-11-26 | Yokohama Rubber Co Ltd:The | Rubber composition |
| DD122255A1 (en) * | 1975-11-14 | 1976-09-20 | ||
| US4057529A (en) * | 1976-02-27 | 1977-11-08 | Wyrough And Loser, Inc. | Rubber compositions having improved adhesion after thermal aging |
| JPS5350246A (en) * | 1976-10-20 | 1978-05-08 | Bridgestone Corp | Rubber composition having good adhesion to metal |
| US4203874A (en) * | 1977-08-15 | 1980-05-20 | The Firestone Tire & Rubber Company | Method, composition and product with improved adhesion between a metal member and a contiguous cured rubber skim stock |
| DE2739949A1 (en) * | 1977-09-05 | 1979-03-15 | Uniroyal Inc | Polyester-rubber bonding agent for tyre cord, etc. - includes metal cpd. which is added to a polyepoxide-poly:isocyanate reaction mixt. |
| JPS5447778A (en) * | 1977-09-22 | 1979-04-14 | Bridgestone Corp | Rubber composition having improved adhesiveness to metal and bonding using it |
| US4244842A (en) * | 1978-02-21 | 1981-01-13 | Ciba-Geigy Corporation | Nickel and cobalt chelate complexes and their use |
| EP0009000A1 (en) * | 1978-08-25 | 1980-03-19 | Ciba-Geigy Ag | Metal salt complexes; their use as agents for bonding vulcanizable elastomers to metallic surfaces |
-
1981
- 1981-03-16 FR FR8105367A patent/FR2501700B1/en not_active Expired
-
1982
- 1982-03-01 BE BE0/207440A patent/BE892320A/en not_active IP Right Cessation
- 1982-03-10 BR BR8201429A patent/BR8201429A/en not_active IP Right Cessation
- 1982-03-11 NL NLAANVRAGE8201023,A patent/NL189862C/en not_active IP Right Cessation
- 1982-03-15 SE SE8201617A patent/SE451589B/en not_active IP Right Cessation
- 1982-03-15 SE SE8201617D patent/SE8201617L/en not_active Application Discontinuation
- 1982-03-15 GB GB8207483A patent/GB2096150B/en not_active Expired
- 1982-03-15 AT AT0102482A patent/AT380690B/en not_active IP Right Cessation
- 1982-03-15 ES ES510427A patent/ES510427A0/en active Granted
- 1982-03-15 IT IT67317/82A patent/IT1156452B/en active
- 1982-03-15 LU LU84013A patent/LU84013A1/en unknown
- 1982-03-16 AU AU81506/82A patent/AU547890B2/en not_active Ceased
- 1982-03-16 AR AR288758A patent/AR226017A1/en active
- 1982-03-16 JP JP57041622A patent/JPS57165431A/en active Granted
- 1982-03-16 CH CH1652/82A patent/CH650267A5/en not_active IP Right Cessation
- 1982-03-16 ZA ZA821753A patent/ZA821753B/en unknown
- 1982-03-16 CA CA000398482A patent/CA1196436A/en not_active Expired
- 1982-03-16 DE DE3209581A patent/DE3209581C2/en not_active Expired
- 1982-03-16 DK DK116682A patent/DK156073C/en not_active IP Right Cessation
-
1984
- 1984-04-18 US US06/601,501 patent/US4549594A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DK116682A (en) | 1982-09-17 |
| ZA821753B (en) | 1983-01-26 |
| DK156073B (en) | 1989-06-19 |
| FR2501700A1 (en) | 1982-09-17 |
| LU84013A1 (en) | 1982-07-08 |
| ATA102482A (en) | 1985-11-15 |
| AU547890B2 (en) | 1985-11-07 |
| BE892320A (en) | 1982-07-01 |
| NL8201023A (en) | 1982-10-18 |
| GB2096150A (en) | 1982-10-13 |
| NL189862B (en) | 1993-03-16 |
| AR226017A1 (en) | 1982-05-14 |
| GB2096150B (en) | 1984-08-01 |
| IT8267317A0 (en) | 1982-03-15 |
| AT380690B (en) | 1986-06-25 |
| US4549594A (en) | 1985-10-29 |
| BR8201429A (en) | 1983-02-01 |
| SE8201617L (en) | 1982-09-17 |
| CA1196436A (en) | 1985-11-05 |
| SE451589B (en) | 1987-10-19 |
| ES8602071A1 (en) | 1985-11-16 |
| NL189862C (en) | 1993-08-16 |
| DK156073C (en) | 1989-11-06 |
| DE3209581A1 (en) | 1982-09-23 |
| JPS57165431A (en) | 1982-10-12 |
| IT1156452B (en) | 1987-02-04 |
| FR2501700B1 (en) | 1985-08-09 |
| CH650267A5 (en) | 1985-07-15 |
| DE3209581C2 (en) | 1985-08-08 |
| AU8150682A (en) | 1982-09-23 |
| ES510427A0 (en) | 1985-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3305841B1 (en) | Rubber composition and tire with tread for combination of low temperature performance and wet traction | |
| EP0307341B1 (en) | A method of preparing pneumatic tire compounds containing syndiotactic-1,2-polybutadiene | |
| US4258770A (en) | Cured rubber skim stock compositions having improved metal adhesion and metal adhesion retention | |
| KR20120050416A (en) | Tires and tread formed from phenol-aromatic-terpene resin | |
| CA2510568C (en) | Rubber compositions and articles thereof having improved metal adhesion and metal adhesion retention with bright steel | |
| CN109749146B (en) | Low-heat-generation rubber composition for tire steel wire belt | |
| US4588766A (en) | Adhesion of rubber to metals | |
| JPH0468337B2 (en) | ||
| JP3323279B2 (en) | Rubber composition for bonding steel cord | |
| JPH0157695B2 (en) | ||
| CA1056972A (en) | Rubber composition | |
| JP3116239B2 (en) | Rubber composition | |
| US10208189B2 (en) | Tire with tread with oxidized carbon black | |
| JP2558863B2 (en) | Method for producing rubber / metal composite material having strong rubber / metal bond | |
| JPH0711052A (en) | Accelerator for binding of rubber to steel cord | |
| JPS6036216B2 (en) | Rubber product | |
| KR101409502B1 (en) | silica dispersion agent of amine type for producing tire | |
| KR100385569B1 (en) | Adhesive rubber composition | |
| KR20220063373A (en) | A composition for a tire tread, and a tire tread manufactured using the composition | |
| JPS60193701A (en) | Steel radial tire | |
| EP0386905B1 (en) | Method of bonding vulcanisable elastomer compositions to metals | |
| JP2020114896A (en) | Rubber composition and pneumatic tire using the same | |
| KR100690378B1 (en) | Rubber composition for steel cord coating of tire | |
| JPS61181843A (en) | Rubber composition improved in adhesiveness to metal | |
| CN111662482B (en) | Vulcanizing agent composition, composition for preparing rubber compound, rubber compound and preparation method thereof, and tire |